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The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure\u2010function relationships of the electrocatalysts\u2019 heterometallic composition. Depending on preparation conditions, the Co\u2010Mn oxide was found to change metal composition during catalysis, while the Ni\u2013Mn oxides maintained the NiMn<jats:sub>3<\/jats:sub> ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn<jats:sub>3<\/jats:sub>O<jats:sub>4<\/jats:sub> cubane\u2010like geometry was maintained in the absence of thermal treatment (<jats:bold>2\u2010Ni<\/jats:bold>). In contrast, the thermally generated <jats:bold>3\u2010Ni<\/jats:bold> develops an oxide\u2010like extended structure. Both <jats:bold>2\u2010Ni<\/jats:bold> and <jats:bold>3\u2010Ni<\/jats:bold> undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen\u2010evolving complex in Photosystem\u2005II, including the MMn<jats:sub>3<\/jats:sub>O<jats:sub>4<\/jats:sub> cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.<\/jats:p>","DOI":"10.1002\/chem.201501104","type":"journal-article","created":{"date-parts":[[2015,8,5]],"date-time":"2015-08-05T20:31:59Z","timestamp":1438806719000},"page":"13420-13430","source":"Crossref","is-referenced-by-count":22,"title":["Molecular Mixed\u2010Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts"],"prefix":"10.1002","volume":"21","author":[{"given":"Sandy","family":"Suseno","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Charles C. 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